Thermochromic rylene dyes

ABSTRACT

Rylene dyes of the general formula I  
                 
 
     where  
     R is hydrogen; unsubstituted or substituted C 1 -C 30 -alkyl, aryl or hetaryl;  
     R′ is unsubstituted or substituted C 2 -C 30 -alkyl or C 5 -C 8 -cycloalkyl, or substituted methyl;  
     n is 0 or 1,  
     their preparation and use for coloring high-molecular-weight organic and inorganic materials, and  
     aminorylene-3,4-dicarboximide of the formula IV as their intermediates.

[0001] The present invention relates to novel rylene dyes of the generalformula I

[0002] where

[0003] R is hydrogen;

[0004]  C₁-C₃₀-alkyl, whose carbon chain may be interrupted by one ormore —O—, —S—, —NR¹—, —CO— and/or —SO₂— groups and which may bemonosubstituted or polysubstituted by cyano, C₁-C₆-alkoxy, aryl, whichmay be substituted by C₁-C₁₈-alkyl or C₁-C₆-alkoxy, and/or a 5- to7-membered heterocyclic radical which is bonded via a nitrogen atom andmay contain further heteroatoms and may be aromatic;

[0005]  aryl or hetaryl, each of which may be monosubstituted orpolysubstituted by C₁-C₁₈-alkyl, C₁-C₆-alkoxy, cyano, —CONHR², —NHCOR²and/or aryl- or hetarylazo, each of which may be substituted byC₁-C₁₀-alkyl, C₁-C₆-alkoxy and/or cyano;

[0006] R′ is C₂-C₃₀-alkyl, whose carbon chain may be interrupted by oneor more —O— and/or —CO— groups and which may be monosubstituted orpolysubstituted by cyano, C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, whose carbonskeleton may be interrupted by one or more —O—, —S— and/or —NR¹— groupsand which may be C₁-C₆-alkyl-substituted, aryl, which may be substitutedby C₁-C₁₈-alkyl or C₁-C₆-alkoxy, and/or a 5- to 7-membered heterocyclicradical which is bonded via a nitrogen atom and which may containfurther heteroatoms and which may be aromatic;

[0007]  methyl, which is monosubstituted or disubstituted by aryl,hetaryl and/or C₅-C₈-cycloalkyl, each of which may be substituted byC₁-C₁₈-alkyl or C₁-C₆-alkoxy;

[0008]  C₅-C₈-cycloalkyl, whose carbon skeleton may be interrupted byone or more —O—, —S— and/or —NR¹— groups and which may bemonosubstituted or polysubstituted by C₁-C₆-alkyl;

[0009] R¹ is hydrogen or C₁-C₆-alkyl;

[0010] R² is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each of which maybe substituted by C₁-C₆-alkyl, C₁-C₆-alkoxy and/or cyano;

[0011] n is 2 or 3,

[0012] and to the preparation of these dyes, and to their use forcoloring high-molecular-weight organic and inorganic materials.

[0013] The present invention furthermore relates to novelaminorylene-3,4-dicarboximides of the general formula IV

[0014] as intermediates for the rylene dyes (I).

[0015] Perylene-3,4-dicarboximides which are substituted on the imidenitrogen atom, unsubstituted perylene-3,4-dicarboximide andperylene-3,4-dicarboximides which are substituted on the peryleneskeleton are suitable not only as pigment precursors, but are themselvesalso advantageously employed as pigments and fluorescent dyes. Theperylene-3,4-dicarboximides substituted on the perylene skeleton whichhave been disclosed hitherto are substituted in the 1,6-, 1,7-, 1,6,9-,1,7,9- and 1,6,7,12-position and also only in the 9-position. Theperylene skeleton in each case carries a halogen atom, in particular abromine atom, in the 9-position (WO-A-96/22331, EP-A-596 292 andWO-A-97/22607 and the references cited therein, and Dyes and Pigments16, pages 19-25 (1991)). EP-A-657 436 and Liebigs Annalen 1995, pages1229-1244, also describe anN-(1-hexylheptyl)-9-aminoperylene-3,4-dicarboximide which is prepared bynitrating the corresponding N-substituted perylene-3,4-dicarboximideusing dinitrogen tetraoxide followed by reduction with metallic iron inthe presence of hydrochloric acid. However, this process is restrictedto perylene-3,4-dicarboximides carrying unsubstituted alkyl groups onthe imide nitrogen atom and gives exclusively isomer mixtures (1- and9-isomers), which are difficult to purify, in low yields. CorrespondingN-substituted 4-aminonaphthalene-1,8-dicarboximides are disclosed inYuki Gosei Kagaku Kyokaishi 12, pages 504-508 (1956) (see ChemicalAbstracts 51:8052 a (1957)).

[0016] EP-A-648 817 describes fluorescent dyes containing imide groupswhose imide nitrogen atom, for reversible solubilization, has beenconverted into a carbamate function, which renders the dye soluble inthe application medium and can be re-cleaved thermally. Inter alia,unsubstituted perylene-3,4-dicarboximide whose NH function is reactedcorrespondingly is also listed here as fluorescent dye. Since thesolubilization takes place via the imide nitrogen atom there is nopossibility of modifying the dye on the nitrogen atom by specificsubstitution. In addition, the hue of the dye does not change on thermalremoval of the alkoxycarbonyl protecting group, and the dye is thereforenot thermochromic.

[0017] WO-A-01/16169, unpublished at the priority date of the presentinvention, describes shorter homologs of the rylene dyes of theinvention based on naphthalene- and perylene-3,4-dicarboxylic acidderivatives. These homologs, however, cover only the shorter-wave colorspace.

[0018] It is an object of the present invention to provide further dyeshaving advantageous applicational properties which can in particular notonly be incorporated readily into the respective application medium andmatched to this medium, but are also thermochromic and absorb in the redand infrared region of the electromagnetic spectrum.

[0019] We have found that this object is achieved by the rylene dyes ofthe formula I defined at the outset.

[0020] Preferred rylene dyes are given in the subclaims.

[0021] We have also found a process for the preparation of the rylenedyes of the general formula I which comprises

[0022] a) reacting a bromorylene-3,4-dicarboximide of the generalformula II

[0023]  with a benzophenonimine of the general formula III

[0024]  where

[0025] R″, R′″, independently of one another, are hydrogen, C₁-C₆-alkylor C₁-C₆-alkoxy and

[0026] x, y, independently of one another, are an integer from 1 to 3,

[0027]  in the presence of an aprotic organic solvent, atransition-metal catalyst system and a base in an aryl-N couplingreaction;

[0028] b) hydrolyzing the resultant ketimine in the presence of an acidand in the presence of a polar, aprotic solvent to give anaminorylene-3,4-dicarboximide of the general formula IV

[0029]  and

[0030] c) subsequently reacting the latter with a dicarbonate of thegeneral formula V

[0031]  in the presence of a polar, aprotic solvent and in the presenceof a base to give the rylene dye I.

[0032] We have also found a process for the preparation ofaminorylene-3,4-dicarboximides of the general formula IV, whichcomprises a) reacting a bromorylene-3,4-dicarboximide of the generalformula II with a benzophenonimine of the general formula III in thepresence of an aprotic organic solvent, a transition-metal catalystsystem and a base in an aryl-N coupling reaction to give thecorresponding ketimine, and b) subsequently hydrolyzing the latter inthe presence of an acid and in the presence of a polar, aprotic solvent.

[0033] In addition, we have found the aminorylene-3,4-dicarboximides ofthe general formula IV as intermediates for the rylene dyes of thegeneral formula I.

[0034] Not least, we have found the use of the rylene dyes of thegeneral formula I for coloring high-molecular-weight organic andinorganic materials.

[0035] All the alkyl groups which occur in the formulae I to V can beeither straight-chain or branched. If the alkyl groups are substituted,they generally carry 1 or 2 substituents. Substituted aromatic radicalscan generally have up to 3, preferably 1 or 2, of said substituents.Preferred aryl radicals are naphthyl and in particular phenyl.

[0036] Examples which may be mentioned of suitable radials R, R′, R″,R′″, R¹ and R² (and their substituents) are detailed below:

[0037] methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl,heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl,decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (theabove names isooctyl, isononyl, isodecyl and isotridecyl are trivialnames and originate from the alcohols obtained in the oxosynthesis);

[0038] 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl,2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl,4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl,4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl,3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 3,6,9,12-tetraoxatridecyl and3,6,9,12-tetraoxatetradecyl;

[0039] 2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl,2-isopropylthioethyl, 2-butylthioethyl, 2- and 3-methylthiopropyl, 2-and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and3-butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-ethylthiobutyl, 2-and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl,4,8-dithianonyl, 3,7-dithiaoctyl, 3,7-dithianonyl, 4,7-dithiaoctyl,4,7-dithianonyl, 2- and 4-butylthiobutyl, 4,8-dithiadecyl,3,6,9-trithiadecyl, 3,6,9-trithiaundecyl, 3,6,9-trithiadodecyl,3,6,9,12-tetrathiatridecyl and 3,6,9,12-tetrathiatetradecyl;

[0040] 2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2-and 3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl,6-methyl-3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-diazaoctyl,3,6-dimethyl-3,6-diazaoctyl, 9-methyl-3,6,9-triazadecyl,3,6,9-trimethyl-3,6,9-triazaundecyl, 12-methyl-3,6,9,12-tetraazatridecyland 3,6,9,12-tetramethyl-3,6,9,12-tetraazatridecyl;

[0041] propan-2-on-1-yl, butan-3-on-1-yl, butan-3-on-2-yl and2-ethylpentan-3-on-1-yl;

[0042] 2-methylsulfonylethyl, 2-ethylsulfonylethyl,2-propylsulfonylethyl, 2-isopropylsulfonylethyl, 2-buthylsulfonylethyl,2- and 3-methylsulfonylpropyl, 2- and 3-ethylsulfonylpropyl, 2- and3-propylsulfonylpropyl, 2- and 3-butylsulfonylpropyl, 2- and4-methylsulfonylbutyl, 2- and 4-ethylsulfonylbutyl, 2- and4-propylsulfonylbutyl and 4-butylsulfonylbutyl;

[0043] cyanomethyl, 2-cyanoethyl, 3-cyanopropyl,2-methyl-3-ethyl-3-cyanopropyl, 7-cyano-7-ethylheptyl and4-methyl-7-methyl-7-cyanoheptyl;

[0044] methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy,sec-butoxy, tert-butoxy, pentoxy, isopentoxy, neopentoxy, tert-pentoxyand hexoxy;

[0045] carbamoyl, methylaminocarbonyl, ethylaminocarbonyl,propylaminocarbonyl, butylaminocarbonyl, pentylaminocarbonyl,hexylaminocarbonyl, heptylaminocarbonyl, octylaminocarbonyl,nonylaminocarbonyl, decylaminocarbonyl and phenylaminocarbonyl;

[0046] formylamino, acetylamino, propionylamino and benzoylamino;

[0047] phenylazo, 2-naphthylazo, 2-pyridylazo and 2-pyrimidylazo;

[0048] phenyl, 2-naphthyl, 2- and 3-pyrryl, 2-, 3- and 4-pyridyl, 2-, 4-and 5-pyrimidyl, 3-, 4- and 5-pyrazolyl, 2-, 4- and 5-imidazolyl, 2-, 4-and 5-thiazolyl, 3-(1,2,4-triazyl), 2-(1,3,5-triazyl), 6-quinaldyl, 3-,5-, 6- and 8-quinolinyl, 2-benzoxazolyl, 2-benzothiazolyl,5-benzothiadiazolyl, 2- and 5-benzimidazolyl and 1- and 5-isoquinolyl;

[0049] 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl,2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl,2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5-and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl,2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 2,5-, 3,5- and2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyl and2,4,6-tri-sec-butylphenyl, 2-, 3- and 4-tert-butylphenyl, 2,4-, 2,5-,3,5- and 2,6-di-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl; 2,3- and4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl,2,4,6-trimethoxyphenyl, 2, 3- and 4-ethoxyphenyl, 2,4-, 2,5-3,5- and2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2,3- and 4-propoxyphenyl,2,4-, 2,5-, 3,5- and 2,6-dipropoxyphenyl, 2,3- and 4-isopropoxyphenyl,2,4-, 2,5-, 3,5- and 2,6-diisopropoxyphenyl and 2,3- and 4-butoxyphenyl;2-, 3- and 4-cyanophenyl; 3- and 4-carboxyphenyl; 3- and4-carboxamidophenyl, 3- and 4-N-methylcarboxamidophenyl and 3- and4-N-ethyl-carboxamidophenyl; 3- and 4-acetylaminophenyl, 3- and4-propionylaminophenyl and 3- and 4-butyrylaminophenyl; 3- and4-N-phenylaminophenyl, 3- and 4-N-(o-tolyl)aminophenyl, 3- and4-N-(m-tolyl)aminophenyl and 3- and 4-N-(p-tolyl)aminophenyl; 3- and4-(2-pyridyl)aminophenyl, 3- and 4-(3-pyridyl)aminophenyl, 3- and4-(4-pyridyl)aminophenyl, 3- and 4-(2-pyrimidyl)aminophenyl and4-(4-pyrimidyl)aminophenyl;

[0050] 4-phenylazophenyl, 4-(1-napthylazo)phenyl,4-(2-naphthylazo)phenyl, 4-(4-naphthylazo)phenyl,4-(2-pyridylazo)phenyl, 4-(3-pyridylazo)phenyl, 4-(4-pyridylazo)phenyl,4-(2-pyrimidylazo)phenyl, 4-(4-pyrimidylazo)phenyl and4-(5-pyrimidylazo)phenyl;

[0051] cyclopentyl, 2- and 3-methylcyclopentyl, 2- and3-ethylcyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3-and 4-ethylcyclohexyl, 3- and 4-propylcyclohexyl, 3- and4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and4-sec-butylcyclohexyl, 3- and 4-tert-butylcyclohexyl, cycloheptyl, 2-,3- and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and4-propylcycloheptyl, 3- and 4-isopropylcycloheptyl, 3- and4-butylcycloheptyl, 3- and 4-sec-butylcycloheptyl, 3- and4-tert-butylcycloheptyl, cyclooctyl, 2-, 3-, 4- and 5-methylcyclooctyl,2-, 3-, 4- and 5-ethylcyclooctyl, 3-, 4- and 5-propylcyclooctyl,2-dioxanyl, 4-morpholinyl, 2- and 3-tetrahydrofuryl, 1-, 2- and3-pyrrolidinyl and 1-, 2-, 3- and 4-piperidyl.

[0052] The rylene dyes of the general formula I can advantageously beprepared by the multistep process according to the invention, in which,in step a) a bromorylene-3,4-dicarboximide of the general formula II isreacted with a benzophenonimine of the general formula III to give aketimine, in step b), the ketimine is hydrolyzed under acidic conditionsto give the aminorylene-3,4-dicarboximide of the general formula IV, andthe latter is subsequently reacted, in step c), with a dicarbonate ofthe formula V to give the rylene dye of the general formula I.

[0053] The terrylene- and/or quaterrylene-3,4-dicarboximides II,brominated in the peri position and used as starting materials in stepa), are known from prior German patent application 101 08 156.1 and maybe prepared by the following, three-stage process described therein:

[0054] a′) one-sided alkaline saponification of an asymmetricrylenetetracarboxylic diimide of the formula VI

[0055]  in which R⁴ is C₅-C₈-cycloalkyl whose carbon framework may beinterrupted by one or more groups —O—, —S— and/or —NR²— and which may besubstituted one or more times by C₁-C₆-alkyl,

[0056]  in the presence of a polar organic solvent,

[0057] b′) one-sided decarboxylation of the rylenetetracarboxylicmonoimide monoanhydride formed in step a′), of the formula VII

[0058]  in the presence of a tertiary nitrogen-basic compound and of atransition metal catalyst, and

[0059] c′) reaction of the peri-unsubstituted rylene-3,4-dicarboximideof the formula VIII

[0060]  with elemental bromine.

[0061] Polar solvents suitable for step a′) of this process are, inparticular, branched C₃-C₆ alcohols, such as isopropanol, tert-butanoland 2-methyl-2-butanol.

[0062] In general, from 40 to 200 g of solvent are employed per g of VI.

[0063] Suitable bases are inorganic bases, especially alkali metal andalkaline earth metal hydroxides, e.g. sodium hydroxide and potassiumhydroxide, which are used preferably in the form of aqueous solutions orsuspensions (generally with a concentration or strength of from 50 to80% by weight), and organic bases, especially alkali metal and alkalineearth metal alkoxides, with preference being given to sodium andpotassium alkoxides, such as sodium methylate, potassium methylate,potassium isopropylate and potassium tert-butylate, which are commonlyused in anhydrous form.

[0064] In general from 5 to 50 equivalents of base, based on VI, arerequired.

[0065] The reaction temperature is generally from 50 to 120° C.,preferably from 60 to 100° C.

[0066] The saponification is normally concluded in from 10 to 40 h.

[0067] In step b′) of this process, the rylene tetracarboxylic monoimidemonohydrides VII are one-sidedly decarboxylated in the presence of atertiary nitrogen-basic compound as solvent and of a transition metalcatalyst.

[0068] Particularly suitable solvents are high-boiling nitrogen bases,e.g. cyclic amides, such as N-methylpyrrolidone, and aromaticheterocycles, such as quinoline, isoguinoline and quinaldine.

[0069] Customary solvent amounts are from 20 to 150 g per g of VII.

[0070] Particularly suitable catalysts are the transition metals copperand zinc and also in particular their organic and inorganic salts, whichare preferably used in anhydrous form.

[0071] Examples of preferred salts are copper(I) oxide, copper(II)oxide, copper(I) chloride, copper(II) acetate, zinc acetate and zincpropionate, particular preference being given to copper(I) oxide andzinc acetate.

[0072] It is of course also possible to use mixtures of said catalysts.

[0073] In general from 50 to 90 mol % of catalyst, based on VII, areemployed.

[0074] The reaction temperature is generally from 100 to 250° C., inparticular from 160 to 200° C. It is advisable to operate using an inertgas atmosphere (e.g. nitrogen).

[0075] The decarboxylation is normally over in from 3 to 20 h.

[0076] Step c′) of this process, the regioselective bromination of therylene-3,4-dicarboximide VIII, is preferably conducted in an aliphaticmonocarboxylic acid, particularly a C₁-C₄-carboxylic acid, such asformic acid, acetic acid, propionic acid, butyric acid or mixturesthereof, or in a halogenated, aliphatic or aromatic solvent, such asmethylene chloride, chloroform or chlorobenzene.

[0077] It is normal to use from 5 to 30 g, preferably from 15 to 25 g,of solvent per g of VIII that is to be brominated.

[0078] In general, the presence of a halogenating catalyst is notnecessary. However, if it is desired to accelerate the brominationreaction (for example by a factor of 1.5 to 2), it is advisable to addelemental iodine, preferably in an amount of from 1 to 5 mol %, based onVIII.

[0079] The molar ratio between bromine and VIII is generally from about1:1 to 5:1, preferably from 3:1 to 4:1.

[0080] The reaction temperature is generally from 0 to 70° C.,preferably from 10 to 40° C.

[0081] Depending on the reactivity of the substrate of the generalformula VIII and the presence or absence of iodine, the bromination isusually complete in from 2 to 12 hours.

[0082] Step a) of the present, inventive process, the reaction of thebromorylene-3,4-dicarboximide II with a benzophenone III in an aryl-Ncoupling reaction to give a ketimine, is conducted in the presence of anaprotic organic solvent, a transition metal catalyst system and a base.

[0083] Suitable benzophenonimines of the general formula III for theketimine formation are, in particular, benzophenonimine, 4,4′-dimethyl-and 4,4′-diethylbenzophenonimine, 2,2′ ,4,4′-tetramethylbenzophenonimineand 4,4′-dimethoxy- and 4,4′-diethoxybenzophenonimine, benzophenonimineitself being preferred.

[0084] In general, from 1 to 4 mol, preferably from 1.5 to 2.5 mol, ofIII are employed per mole of II.

[0085] Particuarly suitable aprotic organic solvents are anhydrous,inert, aromatic solvents, such as benzene and its alkylation products,for example toluene and o-, m- and p-xylene, and mixtures of thesecompounds.

[0086] The amount of solvent is usually from 50 to 300 kg, preferablyfrom 100 to 200 kg, per kg of II.

[0087] Particularly suitable transition-metal catalysts are palladiumcompounds, where palladium(0) and palladium(II) complexes, such astris(dibenzylideneacetone)dipalladium(0),dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) anddichloro(1,5-cyclooctadiene)palladium(II), and palladium(II) acetate maybe mentioned as preferred examples.

[0088] The transition-metal catalyst is usually employed in an amount offrom 0.5 to 5 mol %, especially from 1 to 3 mol %, based on II.

[0089] In addition, a phosphine-based cocatalyst is preferably employed.Preferred examples thereof are bidentate phosphine ligands, such asracemic 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,1′-bis(diphenylphosphino)ferrocene,1,1′-bis(di-o-tolylphosphino)ferrocene,1,1′-bis(di-p-methoxyphenylphosphino)ferrocene and2,2′-bis(di-o-tolylphosphino)-diphenylether, and phosphines which act asmonodentate phosphine ligands, such as tri-o-tolylphosphine,tri-tert-butylphosphine and triphenylphosphine.

[0090] Suitable amounts of cocatalyst are generally from 1 to 5 mol %,preferably from 1 to 3 mol %, based on the transition-metal catalyst.

[0091] Particularly suitable bases are alkali metal amides, especiallyalkali metal di(C₃-C₆-alkyl)amides, and alkali metal alkoxides,especially the alkali metal salts of secondary and tertiary aliphatic(C₃-C₆)-alcohols. Preferred examples of these bases are lithiumdiisopropylamide, sodium diisopropylamide and potassiumdiisopropylamide, and lithium isopropoxide, sodium iospropoxide,potassium isopropoxide, lithium tert-butoxide, sodium tert-butoxide andpotassium tert-butoxide, particular preference being given to sodiumtert-butoxide and potassium tert-butoxide.

[0092] In general, an amount of base which his equimolar to thebenzophenonimine of the general formula III is employed.

[0093] The reaction temperature is usually from 50 to 140° C.,preferably from 70 to 120° C.

[0094] Depending on the reactivity of the brominatedrylene-3,4-dicarboximide of the general formula II and the amount ofcatalyst employed, the reaction time is generally from 10 to 24 hours.

[0095] An advantageous technical procedure in step a) is the following:

[0096] The solvent, catalyst and cocatalyst are initially introducedunder a protective-gas atmosph re, the bromorylene-3,4-dicarboximide ofthe general formula II, the benzophenonimine of the general formula IIIand the base are added successively with stirring, and the mixture isheated at the desired reaction temperature under a protective gas forfrom to 24 hours. After the mixture has been cooled to room temperature,the solid constituents are filtered off, and the solvent is removed bydistillation under reduced pressure.

[0097] The purity of the resultant ketimine is generally adequate forfurther processing. If desired, the crude product can be purifiedfurther by re-precipitation from a mixture of chloroform or methylenechloride and petroleum ether or by column chromatography on silica gelusing chloroform as eluent.

[0098] Step b) of the process according to the invention, the hydrolysisof the ketimine to give aminorylene-3,4-dicarboximide of the generalformula IV, is carried out in the presence of a polar, aprotic solvent.Preferred solvents are aliphatic ethers, where acrylic ethers, such as,in particular, di(C₂-C₄-alkyl)ethers and C₂-C₃-alkyleneglycoldi-C₁-C₂-alkylethers, and cyclic ethers are suitable. The followingparticularly preferred ethers may be mentioned by way of example:diethylether, dipropylether, dibutylether, ethylene glycol dimethyl anddiethyl ether, tetrahydrofuran and dioxane.

[0099] In general, from 80 to 300 kg, preferably from 100 to 200 kg, ofsolvent are employed per kg of ketimine.

[0100] The hydrolysis is preferably carried out using an inorganic acid,such as hydrochloric acid, sulfuric acid, phosphoric acid or nitricacid.

[0101] From 3 to 6 kg of a 2 to 4 normal aqueous solution of the acidare usually employed per kg of ketimine.

[0102] The reaction temperature is generally from 10 to 60° C.,preferably from 20 to 40° C.

[0103] The hydrolysis is generally complete in from 0.5 to 3 hours.

[0104] An advantageous technical procedure in step b) is the following:

[0105] The ketimine is dissolved in the solvent with stirring, themixture is brought to the desired reaction temperature, the aqueous acidis added and the mixture is stirred at this temperature for from 0.5 to3 hours. The remaining acid is subsequently neutralized, for exampleusing concentrated aqueous ammonia and the solvent is removed bydistillation under reduced pressure.

[0106] The following procedure can then be used for further work-up ofthe reaction product:

[0107] The residue is suspended in an excess of dilute aqueous base (forexample ammonia water) and filtered off, the filter material is, ifdesired, stirred repeatedly in a 30- to 50-fold amount of hot aqueousbase (for example semiconcentrated aqueous ammonia) and again filteredoff, and the filter material is washed with water until neutral anddried at 100° C. under reduced pressure. In order to remove benzophenoneand further organic impurities, the dried crude product is subsequentlyextracted with petroleum ether.

[0108] Step c) of the process according to the invention, the reactionof the aminorylenedicarboximide of the general formula IV with adicarbonate of the general formula V to give the rylene dye of thegeneral formula I is carried out in the presence of a polar, aproticsolvent with base catalysis.

[0109] Particularly preferred dicarbonates of the general formula V aredialkyl carbonates, especially di(C₂-C₈-alkyl) dicarbonates, such asdiethyl dicarbonate, dipropyl dicarbonate, diisopropyl dicarbonate,di-n-butyl dicarbonate, di-sec-butyl dicarbonate, di-tert-butyldicarbonate, di-tert-pentyl dicarbonate and bis(2-ethylhexyl)dicarbonate, dicycloalkyl dicarbonates, especially di(C₅-C₈-cycloalkyl)dicarbonates, such as dicyclopentyl dicarbonate, dicyclohexyldicarbonate and dicycloheptyl dicarbonate, dicycloalkylalkyldicarbonates, such as bis(1- and 2-cyclohexylethyl) dicarbonate andbis(1,2- and 3-cyclohexylpropyl) dicarbonate, diaralkyl dicarbonates,especially diphenyl-C₁-C₄-alkyl dicarbonates, such as dibenzyldicarbonate, bis(1- and 2-phenylethyl) dicarbonate and bis(1-, 240 and3-phenylpropyl) dicarbonate, and diphenyldicycloalkyl-(C₁-C₄-alkyl)dicarbonates, such as bis(1- and 2-cyclohexyl-2-phenyl) dicarbonate,bis(1-, 2- and 3-cyclohexyl-2-phenyl) dicarbonate and bis(1-, 2- and3-cyclohexyl-3-phenyl) dicarbonate.

[0110] In general, from 2 to 5 mol, preferably from 3 to 4 mol of V areemployed per mole of IV.

[0111] Particularly suitable polar, aprotic solvents are the ethersmentioned for step b), which are advantageously used in anhydrous(dried) form.

[0112] The amount of solvent is usually from 80 to 300 kg, preferablyfrom 120 to 200 kg, per kg of IV.

[0113] Particularly suitable bases are nitrogen bases, especiallytertiary aliphatic amines, preferably tri(C₁-C₄-alkyl)amines, whosealkyl radicals may be identical or different and which are preferablyused in combination with dialkylamino-substituted pyridines. Veryparticular preference is given to combinations oftri(C₂-C₄-alkyl)amines, such as triethylamine, diisopropylethylamine andtributylamine, with 4-(N,N-dimethylamino)pyridine in a molar ratio offrom 4:1 to 1:1, in particular of about 2:1.

[0114] In general, from 5 to 20 mol %, preferably about 10 mol % ofbase, based on V, are employed.

[0115] The reaction temperature is generally from 20 to 70° C.,preferably from 35 to 50° C.

[0116] The reaction time is usually form 4 to 20 hours.

[0117] An advantageous technical procedure in step c) is the following:

[0118] The solvents, the aminorylene-3,4-dicarboximide of generalformula IV and the base are initially introduced under a protective-gasatmosphere, the dicarbonate of the general formula V is added, and themixture is stirred at the desired reaction temperature under aprotective gas for from 4 to 20 hours. In order to work up the rylenedye of the general formula I, from about 70 to 80% by vol. of thesolvent are subsequently removed by distillation under reduced pressure,a 2- to 4-fold amount of an aliphatic alcohol, for example methanol, isslowly added, and the precipitation of the rylene dye of the generalformula I is completed by cooling to from 3 to 6° C., and the dye of thegeneral formula I is filtered off and dried at 100° C. under reducedpressure.

[0119] The purity of the resultant rylene dyes of the general formula Iis generally >97% and is generally adequate for use. For particularrequirements, the purity can be increased by recrystallization from ahalogenated hydrocarbon, such as methylenechloride or chloroform, or anaromatic solvent, such as benzene, toluene or xylene, or by columnchromatography on silica gel using chloroform as eluent.

[0120] The process according to the invention enables the preparation ofthe rylene dyes of the general formula I and their intermediates in anadvantageous economical manner. The purity of the products obtained inthe individual process steps is generally >95% without furtherpurification, and the yield over all process steps, in each case basedon the rylene-3,4-dicarboximide derivative employed, is generally >60%.

[0121] The rylene dyes of the general formula I according to theinvention are highly suitable for homogeneous coloring ofhigh-molecular-weight organic and inorganic materials, in particular,for example, plastics, especially thermoplastics, surface coatings andprinting inks, and oxidic layer systems.

[0122] A particularly advantageous property of the rylene dyes of thegeneral formula I according to the invention is their thermochromicity,i.e. the irreversible conversion of the dyes from a molecular specieshaving a primary color A into a structurally different species having asecondary color B. The thermochromic effect is induced by warming thecolored material to temperatures above the conversion temperature of therylene dye of the general formula I. The primary and/or secondary colorof the colored material can in addition be varied in a simple manner byemploying rylene dyes of the general formula I according to theinvention in the form of a mixture with one another, with thethermochromic rylene dyes disclosed in WO-A-01/16109, unpublished at thepriority date of the present invention, and/or with conventionalpigments and dyes.

[0123] The thermochromicity of the rylene dyes of the general formula Iaccording to the invention can in addition advantageously be utilizedfor the production of laser-markable or laser-inscribable colorings.Through a suitable choice of the substituent R′, the conversiontemperature of the rylene dyes of the general formula I can be setspecifically for this application, which was unexpected. Thus, theconversion temperatures of rylene dyes of the formula I according to theinvention in which R′ is primary or secondary alkyl or aralkyl aregenerally >280° C. These rylene dyes of the general formula I can beincorporated into classical thermoplastics (for example polystyrene,poly(acrylonitrile-butadiene-styrene), poly(styrene-acrylonitrile),polycarbonate, polymethyl methacrylate or polyethylene terephthalate) ina conventional manner (for example by extrusion or injection molding)and used for industrial laser marking or inscription.

[0124] A laser-markable or laser-inscribable color can be produced usingthe rylene dyes of the general formula I according to the invention (ormixtures thereof with one another, with the thermochromic rylene dyesdisclosed in WO-A-01/16109, unpublished at the priority date of tepresent invention, and/or with other colorants) in combination with oneor more transparent or translucent, organic or inorganic (N)IR absorbershaving, in particular, a neutral or only weak inherent color in thevisible region which converts the incident (N)IR laser energy into thethermal energy needed for the thermochromic conversion.

[0125] For this purpose, conventional, commercially available (N)IRabsorbers, for example those from the classes of the methines,azamethines, transition-metal dithiolenes, squaric acid derivatives,phthalocyanines, naphthalocyanines, amidinium and iminium salts and inparticular quaterrylene tetracarboxylic acid derivatives can be used.For use together with semiconductor lasers, particular preference isgiven to absorbers having an absorption maximum at from 780 to 850 nm,and for use together with conventional Nd-YAG lasers, particularpreference is given to absorbers having an absorption maximum at about1064 nm, in each case having a gram absorptivity of at least 50 at theabsorption maximum.

EXAMPLES

[0126] A) Preparation of rylene dyes of the formula I according to theinvention

[0127] a) Preparation of the ketimines

Examples 1 to 6

[0128] A solution, stirred under a protective gas, of k mmol of thetransition-metal catalyst tris(benzylideneacetone)dipalladium(0) and cμmol of the cocatalyst 2,2″-bis(diphenylphosphino)-1,1′-binaphthyl(racemate) in a₁ l of anhydrous toluene was heated at 100° C. for 12 hafter addition of x₁ g (18 mmol) of themonobromorylene-3,4-dicarboximide of the general formula II, 6.52 g (36mmol) of benzophenonimine and 3.46 g of sodium tert-butoxide.

[0129] After the mixture had been cooled to room temperature, theinsoluble constituents had been filtered off and the solvents had beenremoved by distillation under reduced pressure, the crude product wasdissolved in as little chloroform or methylene chloride as possible withgentle warming. After filtration, the product was re-precipitated bycareful addition of a five-fold amount of petroleum ether (boiling range60-90° C.), filtered off and dried at 100° C. under reduced pressure.

[0130] Further details on these experiments and their results are shownin Table 1. TABLE 1 x₁ k C a₁ Yield m.p. Ex. [g]Bromorylene-3,4-dicarboximide II [mmol] [μmol] [l] [g]/[%] Appearance [°C.] 1 12.5 11-Bromo-N-dodecylterrylene- 0.35 5.5 1.8 11.4/80blue-green, >300 3,4-dicarboximide microcrystalline 2 11.411-Bromo-N-(p-methoxyphenyl)terry- 0.35 5.5 1.8 11.6/88 blue-green, >300lene-3,4-dicarboximide microcrystalline 3 12.311-Bromo-N-(2,6-diisopropylphenyl)- 0.35 5.5 1.8 12.0/85blue-green, >300 terrylene-3,4-dicarboximide crystalline 4 14.713-Bromo-N-dodecylquaterrylene-3,4- 0.50 8.0 2.0 13.0/79black-brown, >300 dicarboximide crystalline 5 13.613-Bromo-N-(p-methoxyphenyl)quater- 0.50 8.0 2.0 13.2/86black-brown, >300 rylene-3,4-dicarboximide crystalline 6 14.613-Bromo-N-(2,6-diisopropylphenyl)- 0.50 10.0 2.0 12.9/79black-brown, >300 quaterrylene-3,4-dicarboximide crystalline

[0131] Analytical data for Example 1:

[0132] 11-(Diphenylmethyleneimino)-N-dodecylterrylene-3,4-dicarboximide:

[0133] Elemental analysis (% by weight calc./found): C: 86.3/86.1; H:6.1/6.2; N: 3.5/3.5; 0:4.0/4.1;

[0134] Mass (FD, 8 kV): m/e=792.4 (M⁺, 100%).

[0135] Analytical data for Example 2:

[0136]11-(Diphenylmethyleneimino)-N-(p-methoxyphenyl)terrylene-3,4-dicarboximide:

[0137] Elemental analysis (% by weight calc./found): C: 85.5/85.4; H:4.1/4.0; N: 3.8/3.9; O: 6.6/6.7;

[0138] Mass (FD, 8 kV): m/e=730.4 (M⁺, 100%).

[0139] Analytical data for Example 3:

[0140]11-(Diphenylmethyleneimino)-N-(2,6-diisopropylphenyl)terrylene-3,4-dicarboximide:

[0141] Elemental analysis (% by weight calc./found): C: 87.2/87.0; H:5.1/5.2; N: 3.6/3.6; O: 4.1/4.2;

[0142] Mass (FD, 8 kV): m/e=784.3 (M⁺, 100%).

[0143] Analytical data for Example 4:

[0144]13-(Diphenylmethyleneimino)-N-dodecylquaterrylene-3,4-dicarboximide:

[0145] Elemental analysis (% by weight calc./found): C: 87.7/87.4; H:5.7/5.8; N: 3.0/3.1; O: 3.5/3.7;

[0146] Mass (FD, 8 kV): m/e=916.4 (M⁺, 100%).

[0147] Analytical data for Example 5:

[0148]13-(Diphenylmethyleneimino)-N-(p-methoxyphenyl)quaterrylene-3,4-dicarboximide:

[0149] Elemental analysis (% by weight calc./found): C: 87.1/87.3; H:4.0/3.9; N: 3.3/3.3; O: 5.6/5.5;

[0150] Mass (FD, 8 kV): m/e=854.2 (M⁺, 100%).

[0151] Analytical data for Example 6:

[0152]13-(Diphenylmethyleneimino)-N-(2,6-diisopropylphenyl)-quaterrylene-3,4-dicarboximide:

[0153] Elemental analysis (% by weight calc./found): C: 88.5/88.0; H:4.9/5.0; N: 3.1/3.0; O: 3.5/3.9;

[0154] Mass (FD, 8 kV): m/e=908.3 (M⁺, 100%).

[0155] b) Preparation of aminorylene-3,4-dicarboximide IV

Examples 7 to 12

[0156] A solution of 10 g (x₂ nmol) of the ketimine from Examples 1 to 6in a₂ 1 of 1,4-dioxane was stirred at T₂° C. for t₂ hours after additionof 50 ml of 2 molar aqueous hydrochloric acid.

[0157] After the reaction mixture has been neutralized using 25%strength by weight aqueous ammonia solution and the solvent has beenremoved by distillation under reduced pressure, the residue wassuspended in a mixture of 1 l of water and 50 ml of concentrated aqueousammonia solution in order to remove inorganic impurities, filtered off,again suspended twice, with interim filtration, in 1 l of hot 20%strength aqueous ammonia solution each time and then filtered. After hotextraction with petroleum ether (boiling range 60-90°⁹C.), the crudeproduct was subsequently freed from benzophenone and other organicimpurities and then dried at 100° C. under reduced pressure.

[0158] Further details on these experiments and their results are shownin Table 2. TABLE 2 x₂ a₂ t₂ T₂ Yield m.p. Ex. [mmol] Ketimine from Ex.[l] [h] [° C.] [g]/[%] Appearance [° C.] 7 12.6 1 1.2 1.0 30 7.5/95blue-green, >300 crystalline 8 13.7 2 1.2 1.0 30 7.3/94 blue-green, >300crystalline 9 12.7 3 1.2 1.0 30 7.3/92 blue-green, >300 microcrystalline10 10.9 4 1.8 1.5 40 7.5/91 black-brown, >300 crystalline 11 11.7 5 1.81.5 40 7.6/94 black-brown, >300 crystalline 12 11.0 6 1.8 1.5 40 7.6/93black-brown, >300 crystalline

[0159] Analytical data for Example 7:

[0160] 11-Amino-N-dodecylterrylene-3,4-dicarboximide:

[0161] Elemental analysis (% by weight calc./found): C: 84.0/84.2; H:6.4/6.5; N: 4.5/4.3; O: 5.1/4.9;

[0162] Mass (FD, 8 kV): m/e=628.4 (M⁺, 100%).

[0163] Analytical data for Example 8:

[0164] 11-Amino-N-(p-methoxyphenyl)terrylene-3,4-dicarboximide:

[0165] Elemental analysis (% by weight calc./found): C: 82.7/82.3; H:3.9/4.1; N: 4.9/5.1; O: 8.5/8.4;

[0166] Mass (FD, 8 kv): m/e=566.2 (M⁺, 100%).

[0167] Analytical data for Example 9

[0168] 11-Amino-N-(2,6-diisopropylphenyl)terrylene-3,4-dicarboximide:

[0169] Elemental analysis (% by weight calc./found): C: 87.2/87.0; H:5.1/5.2; N: 3.6/3.6; O: 4.1/4.2;

[0170] Mass (FD, 8 kV): m/e=620.3 (M⁺, 100%).

[0171] Analytical data for Example 10

[0172] 13-Amino-N-dodecylquaterrylene-3,4-dicarboximide:

[0173] Elemental analysis (% by weight calc./found): C: 86.1/86.4; H:5.9/5.7; N: 3.7/3.7; O: 4.3/4.2;

[0174] Mass (FD, 8 kV): m/e=752.6 (M⁺, 100%).

[0175] Analytical data for Example 11

[0176] 13-Amino-N-(p-methoxyphenyl)quaterrylene-3,4-dicarboximide:

[0177] Elemental analysis (% by weight calc./found): C: 85.2/85.2; H:3.8/3.9; N: 4.1/4.0; O: 7.0/6.9;

[0178] Mass (FD, 8 kV): m/e=690.3 (M⁺, 100%).

[0179] Analytical data for Example 12

[0180] 13-Amino-N-(2,6-diisopropylphenyl)quaterrylene-3,4-dicarboximide:

[0181] Elemental analysis (% by weight calc./found): C: 88.5/88.0; H:4.9/5.0; N: 3.1/3.0; O: 3.5/3.9;

[0182] Mass (FD, 8 kV): m/e=744.4 (M⁺, 100%).

[0183] c) Preparation of rylene dyes of the formula I

Examples 13 to 25

[0184] A solution, stirred under a protective gas, of 49 mg (0.4 mmol)of 4-(N,N-dimethylamino)pyridine, 408 mg (0.8 mmol) of triethylamine andx₃ g (2 mmol) of the aminorylene-3,4-dicarboximide from Examples 7 to 12in 200 ml of anhydrous dioxane was heated at 45° C. for t₃ hours afteraddition of y g (8 mmol) of the dicarbonate of the formula V.

[0185] After 80% by vol. of the solvent had been removed by thedistillation under reduced pressure, the precipitation of the productwas completed by slow addition of 500 ml of methanol and cooling to from3 to 6° C. The precipitated product was filtered off, washed withmethanol and dried at 100° C. under reduced pressure.

[0186] The melting points of all rylene dyes of the formula I obtainedwere above the thermal conversion temperature (elimination of CO₂ andalkene or aralkene).

[0187] Further details on these experiments and their results are shownin Table 3. TABLE 3 Amino- rylene-3,4- x₃ dicarboximide IV y t₃ YieldEx. [g] from Ex. [g] Dicarbonate V [h] [g]/[%] Appearance 13 1.26 7 1.30Diethyl dicarbonate 10 1.19/77 deep blue, microcrystalline 14 1.13 81.75 Di-sec-butyl 10 1.23/80 deep blue, dicarbonate microcrystalline 151.24 9 1.30 Diethyl dicarbonate 10 1.19/78 deep blue, microcrystalline16 1.24 9 1.75 Di-n-butyl 10 1.23/75 deep blue, dicarbonatemicrocrystalline 17 1.24 9 1.75 Di-tert-butyl 10 1.38/84 deep blue,dicarbonate microcrystalline 18 1.24 9 2.29 Dibenzyl 10 1.40/79 deepblue, dicarbonate microcrystalline 19 1.51 10 1.75 Di-tert-butyl 101.62/85 blue-green, dicarbonate microcrystalline 20 1.38 11 1.30 Diethyldicarbonate 6 1.42/85 blue-green, microcrystalline 21 1.49 12 1.30Diethyl dicarbonate 6 1.49/84 blue-green, microcrystalline 22 1.49 121.75 Di-n-butyl 6 1.51/80 blue-green, dicarbonate microcrystalline 231.49 12 1.75 Di-sec-butyl 6 1.55/82 blue-green, dicarbonatemicrocrystalline 24 1.49 12 1.75 Di-tert-butyl 6 1.59/84 blue-green,dicarbonate microcrystalline 25 1.49 12 2.29 Dibenzyl 6 1.60/79blue-green, dicarbonate microcrystalline

[0188] Analytical data for Example 13:

[0189]11-(Diethoxycarbonyl)amino-N-(dodecyl)terrylene-3,4-dicarboximide:

[0190] Elemental analysis (% by weight calc./found): C: 77.7/77.7; H:6.3/6.5; N: 3.6/3.5; O: 12.4/12.2;

[0191] Mass (MALDI-TOF): m/e=772.2 (M⁺, 100%); IR (KBr): ν=1698 (s,C═O), 1665 (s, C═O), 1500 (s) cm⁻¹; UV/VIS (NMP): λ_(max) (ε)=580(44000), 646 (49900) nm.

[0192] Analytical data for Example 14:

[0193]11-(Di-sec-butoxycarbonyl)amino-N-(4-methoxyphenyl)terrylene-3,4-dicarboximide:

[0194] Elemental analysis (% by weight calc./found): C: 76.8/76.7; H:5.0/4.9; N: 3.7/3.7; O: 14.6/14.7;

[0195] Mass (MALDI-TOF): m/e=766.6 (M⁺, 100%); IR (KBr): ν=1701 (s,C═O), 1668 (s, C═O) cm⁻¹; UV/VIS (NMP): λ_(max) (ε)=576 (44370), 639(43530) nm.

[0196] Analytical data for Example 15:

[0197]11-(Diethoxycarbonyl)amino-N-(2,6-diisopropylphenyl)terrylene-3,4-dicarboximide:

[0198] Elemental analysis (% by weight calc./found): C: 78.5/78.3; H:5.3/5.3; N: 3.65/3.7; O: 12.55/12.7;

[0199] Mass (MALDI-TOF): m/e=764.3 (M⁺, 100%); IR (KBr): ν=1700 (s,c═O), 1666 (s, C═O), 1501 (s) cm⁻¹; UV/VIS (NMP): λ_(max) (ε)=577(45080), 644 (46110) nm.

[0200] Analytical data for Example 16:

[0201]11-(Di-n-butoxycarbonyl)amino-N-(2,6-diisopropylphenyl)terrylene-3,4-dicarboximide:

[0202] Elemental analysis (% by weight calc./found): C: 79.0/79.3; H:5.9/5.8; N: 3.4/3.5; O: 11.7/11.4;

[0203] Mass (MALDI-TOF): m/e=820.1 (M⁺, 100%); IR (KBr): ν=1702 (s,C═O), 1667 (s, C═O), 1499 (s) cm⁻¹; UV/VIS (NMP): λ_(max) (ε)=577(43980), 645 (44230) nm.

[0204] Analytical data for Example 17:

[0205]11-(Di-tert-butoxycarbonyl)amino-N-(2,6-diisopropylphenyl)-terrylene-3,4-dicarboximide:

[0206] Elemental analysis (% by weight calc./found): C: 79.0/78.8; H:5.9/6.0; N: 3.4/3.5; O: 11.7/11.7;

[0207] Mass (MALDI-TOF): m/e=820.5 (M⁺, 100%); IR (KBr): ν=1749 (s,C═O), 1702 (s, C═O), 1664 (s, C═O), 1594 (s, C═O) cm⁻¹; UV/VIS (NMP):λ_(max) (ε)=579 (44270), 643 (44120) nm.

[0208] Analytical data for Example 18:

[0209]11-(Dibenzyloxycarbonyl)amino-N-(2,6-diisopropylphenyl)-terrylene-3,4-dicarboximide:

[0210] Elemental analysis (% by weight calc./found): C: 81.1/80.7; H:5.0/5.1; N: 3.2/3.2; O: 10.8/11.0;

[0211] Mass (MALDI-TOF): m/e=888.6 (M⁺, 100%); IR (KBr): ν=1700 (s,C═O), 1665 (s, C═O), 1498 (s) cm⁻¹; UV/VIS (NMP): λ_(max) (ε)=577(43980), 645 (46800) nm.

[0212] Analytical data for Example 19:

[0213]13-(Di-tert-butoxycarbonyl)amino-N-(dodecyl)quaterrylene-3,4-dicarboximide:

[0214] Elemental analysis (% by weight calc./found): C: 80.7/81.0; H:6.3/6.1; N: 2.9/2.8; O: 10.1/10.1;

[0215] Mass (MALDI-TOF): m/e=952.2 (M⁺, 100%); IR (KBr): ν=1748 (s,C═O), 1699 (s, C═O), 1665 (s, C═O), 1593 (s, C═O) cm⁻¹; UV/VIS (NMP):λ_(max) (ε)=680 (75000), 744 (78760) nm.

[0216] Analytical data for Example 20:

[0217]13-(Diethoxycarbonyl)amino-N-(4-methoxyphenyl)quaterrylene-3,4-dicarboximide:

[0218] Elemental analysis (% by weight calc./found): C: 79.1/78.7; H:4.1/4.3; N: 3.4/3.5; O: 13.4/13.4;

[0219] Mass (MALDI-TOF): m/e=834.4 (M⁺, 100%); IR (KBr): ν=1700 (s,C═O), 1667 (s, C═O), 1504 (s) cm⁻¹; UV/VIS (NMP): λ_(max) (ε)=677(75580), 738 (73920) nm.

[0220] Analytical data for Example 21:

[0221]13-(Diethoxycarbonyl)amino-N-(2,6-diisopropylphenyl)quaterrylene-3,4-dicarboximide:

[0222] Elemental analysis (% by weight calc./found): C: 81.05/81.2; H:5.0/5.0; N: 3.15/3.1; O: 10.8/10.7;

[0223] Mass (FD, 8 kV): m/e=888.4 (M⁺, 100%); IR (KBr): ν=1701 (s, C═O),1667 (s, C═O), 1502 (s) cm⁻¹; UV/VIS (NMP): λ_(max) (ε)=678 (74080), 742(77640) nm.

[0224] Analytical data for Example 22:

[0225]13-(Di-n-butoxycarbonyl)amino-N-(2,6-diisopropylphenyl)-quaterrylene-3,4-dicarboximide:

[0226] Elemental analysis (% by weight calc./found): C: 81.3/81.0; H:5.5/6.0; N: 3.0/3.0; O: 10.2/10.0;

[0227] Mass (FD, 8 kV): m/e=944.3 (M⁺, 100%); IR (KBr): ν=1701 (s, C═O),1668 (s, C═O), 1504 (s) cm⁻¹; UV/VIS (NMP): λ_(max) (ε)=678 (72840), 741(75210) nm.

[0228] Analytical Data for Example 23:

[0229]13-(Di-sec-butoxycarbonyl)amino-N-(2,6-diisopropylphenyl)-quaterrylene-3,4-dicarboximide:

[0230] Elemental analysis (% by weight calc./found): C: 81.3/81.1; H:5.6/5.4; N: 3.0/3.1; O: 10.1/10.3;

[0231] Mass (FD, 8 kV): m/e=944.2 (M⁺, 100%); IR (KBr): ν=1702 (s, C═O),1666 (s, C═O) cm⁻¹; UV/VIS (NMP): λ_(max) (ε)=679 (73050), 740 (74990)nm.

[0232] Analytical data for Example 24:

[0233]13-(Di-tert-butoxycarbonyl)amino-N-(2,6-diisopropylphenyl)-quaterrylene-3,4-dicarboximide:

[0234] Elemental analysis (% by weight calc./found): C: 81.3/81.0; H:5.6/5.9; N: 3.0/3.0; O: 10.1/10.1;

[0235] Mass (FD, 8 kV): m/e=944.4 (M⁺, 100%); IR (KBr): ν=1750 (s, C═O),1700 (s, C═O), 1665 (s, C═O), 1593 (s, C═O) cm⁻¹; UV/VIS (NMP): λ_(max)(ε)=680 (73820), 745 (73670) nm.

[0236] Analytical data for Example 25:

[0237]13-(Dibenzyloxycarbonyl)amino-N-(2,6-diisopropylphenyl)-quaterrylene-3,4-dicarboximide:

[0238] Elemental analysis (% by weight calc./found): C: 83.0/83.3; H:4.8/5.0; N: 2.8/2.7; O: 9.5/9.0;

[0239] Mass (FD, 8 kV): m/e=1012.7 (M⁺, 100%); IR (KBr): ν=1699 (s,C═O), 1666 (s, C═O), 1501 (s) cm⁻¹; UV/VIS (NMP): λ_(max) (ε)=678(73550), 742 (75800) nm.

[0240] B) Use of rylene dyes of the formula I according to the invention

[0241] a) Preparation of high-molecular-weight materials with athermochromic coloring.

[0242] For the preparation of thermoplastics with a thermochromiccoloring, in each case x g of the dye of the formula I and, if desired,z g of the transparent pigment P or of one of the thermochromic dyes Ffrom WO-A-01/16109, unpublished at the priority date of the presentinvention, were mixed with 100 g of one of the matrix polymers

[0243] PS: Polystyrene 144C crystal clear (BASF)

[0244] PMMA: Polymethyl methacrylate molding composition 7N crystalclear (Röhm) or

[0245] PC: Polycarbonate Makrolone® 2858 (Bayer)

[0246] and converted into a semi-finished product in a conventionalmanner by extrusion and injection molding.

[0247] In order to produce thermochromic surface coatings, a mixture ofin each case x g of the dye of the formula I and 100 g of asolvent-based alkyd-melamine baking enamel (45% by weight of solidscontent) was shaken with 150 g of glass beads (diameter 3 mm) for 30minutes in a Skandex instrument, then applied to metal sheeting using aknife coater and baked for 30 minutes at 130° C. (film thickness in thedried state 55±5 μm).

[0248] The thermochromic color change (primary color→secondary color) ofthe colored polymeric systems was induced by heating for 15 minutes atthe respective conversion temperature T° C.

[0249] Further details on these experiments and their results are shownin Table 4. TABLE 4 Pigment P x Rylene dye z or Polymeric PrimarySecondary T Ex. [g] I from Ex. [g] thermochromic dye F system colorcolor [° C.] 26 0.2 14 — — PS deep blue green 300 27 0.2 15 — — PS deepblue green 340 28 0.2 15 — — PMMA deep blue green 360 29 0.2 15 — — PCdeep blue green 360 30 0.2 17 — — PS deep blue green 220 31 5.0 17 — —varnish deep blue green 190 32 0.2 21 — — PS blue-green pale gray 340 330.2 21 — — PMMA blue-green pale gray 360 34 0.2 21 — — PC blue-greenpale gray 370 35 0.2 22 — — PS blue-green pale gray 310 36 0.2 23 — — PSblue-green pale gray 330 37 0.2 24 — — PS blue-green pale gray 220 385.0 24 — — varnish blue-green pale gray 190 39 0.1 15 0.2254-(Diethoxycarbonyl)amino-N- PS deep blue yellow- 340(2,6-diisopropylphenyl)- green naphthalene-1,8-dicarboximide 40 0.1 210.225 4-(Diethoxycarbonyl)amino-N- PS blue-green yellow- 340(2,6-diisopropylphenyl)- orange naphthalene-1,8-dicarboximide 41 0.1 150.150 9-(Diethoxycarbonyl)amino-N- PS deep blue violet 340(2,6-diisopropylphenyl)perylene- 3,4-dicarboximide 42 0.1 21 0.1509-(Diethoxycarbonyl)amino-N- PS brown violet 340(2,6-diisopropylphenyl)perylene- 3,4-dicarboximide 43 0.2 15 0.200 C.I.Pigment Red 149 PS violet gray-brown 340 (Paliogen ® Rot K 3580) 44 0.221 0.200 C.I. Pigment Red 149 PS brown red 340 (Paliogen ® Rot K 3580)45 0.1 15 0.200 C.I. Pigment Yellow 138 PS green yellow- 340 (Paliotol ®Gelb K 0961) brown 46 0.1 21 0.200 C.I. Pigment Yellow 138 PS blue-greenyellow 340 (Paliotol ® Gelb K 0961)

[0250] b) Production of laser-markable or laser-inscribable colorings

[0251] In order to produce laser-markable or laser-inscribablecolorings, the dyes or dye mixtures from Examples 28, 33, 39 or 41 wereincorporated into PMMA (Examples 28 and 33) or PS (Examples 39 and 41)as described under a), but with addition of y g of the (near) infraredabsorber A.

[0252] The colored semi-finished product was subsequently marked usingan Nd-YAG laser (emission wavelength of 1064 nm, nominal laser power 40watts; scanning rate 1000 mm/s; Examples 47 and 50) or with asemiconductor laser diode (emission wavelength of 780 nm, nominal laserpower 1 watt, scanning rate 100 mm/s; Examples 51 to 54).

[0253] Further details on these experiments and their results are shownin Table 5. TABLE 5 Dyes I or mix- y Color of the Background Ex. turesfrom Ex. [g] (N)IR absorber A mark color 47 28 0.010 (N)IR-SenzitizingDye IR 1060-1 green deep blue (methine dye; Esprit Inc.) 48 33 0.010(N)IR-Senzitizing Dye IR 1060-1 palegray blue-green (methine dye; EspritInc.) 49 39 0.010 (N)IR-Senzitizing Dye IR 1060-1 yellow-green deep blue(methine dye; Esprit Inc.) 50 41 0.010 (N)IR-Senzitizing Dye IR 1060-1violet deep blue (methine dye; Esprit Inc.) 51 28 0.005(N)IR-Senzitizing Dye IR 800-1 yellow-green deep blue (cyanine dye;Esprit Inc.) 52 39 0.005 (N)IR-Senzitizing Dye IR 800-1 yellow-greenblue-green (cyanine dye; Esprit Inc.) 53 33 0.010N,N′-Bis(2,6-diisopropylphenyl)- pale turquoise blue-greenquaterrylene-3,4:13,14-tetra- carboxylic diimide 54 41 0.010N,N′-Bis(2,6-diisopropylphenyl)- violet deep bluequaterrylene-3,4:13,14-tetra- carboxylic diimide

We claim:
 1. A rylene dye of the general formula I

where R is hydrogen;  C₃-C₃₀-alkyl, whose carbon chain may beinterrupted by one or more —O—, —S—, —NR¹—, —CO— and/or —SO₂— groups andwhich may be monosubstituted or polysubstituted by cyano, C₁-C₆-alkoxy,aryl, which may be substituted by C₁-C₁₈-alkyl or C₁-C₆-alkoxy, and/or a5- to 7-membered heterocyclic radical which is bonded via a nitrogenatom and may contain further heteroatoms and may be aromatic;  aryl orhetaryl, each of which may be monosubstituted or polysubstituted byC₁-C₁₈-alkyl, C₁-C₆-alkoxy, cyano, —CONHR², —NHCOR² and/or aryl- orhetarylazo, each of which may be substituted by C₁-C₁₀-alkyl,C₁-C₆-alkoxy and/or cyano; R′ is C₂-C₃₀-alkyl, whose carbon chain may beinterrupted by one or more —O— and/or —CO— groups and which may bemonosubstituted or polysubstituted by cyano, C₁-C₆-alkoxy,C₅-C₈-cycloalkyl, whose carbon skeleton may be interrupted by one ormore —O—, —S— and/or —NR¹ groups and which may beC₁-C₆-alkyl-substituted, aryl, which may be substituted by C₁-C₁₈-alkylor C₁-C₆-alkoxy, and/or a 5- to 7-membered heterocyclic radical which isbonded via a nitrogen atom and which may contain further heteroatoms andwhich may be aromatic;  methyl, which is monosubstituted ordisubstituted by aryl, hetaryl and/or C₅-C₈-cycloalkyl, each of whichmay be substituted by C₁-C₁₈-alkyl or C₁-C₆-alkoxy;  C₅-CB-cycloalkyl,whose carbon skeleton may be interrupted by one or more —O—, —S— and/or—NR¹— groups and which may be monosubstituted or polysubstituted byC₁-C₆-alkyl; R¹ is hydrogen or C₁-C₆-alkyl; R² is hydrogen;C₁-C₁₈-alkyl; aryl or hetaryl, each of which may be substituted byC₁-C₆-alkyl, C₁-C₆-alkoxy and/or cyano; n is 2 or
 3. 2. A rylene dye ofthe formula I as claimed in claim 1, where R is hydrogen;  C₁-C₃₀-alkyl,whose carbon chain may be interrupted by one or more —O— and/or —CO—groups which may be monosubstituted or polysubstituted by cyano,C₁-C₆-alkoxy, aryl, which may be substituted by C₁-C₁₈-alkyl orC₁-C₆-alkoxy, and/or a 5- to 7-membered heterocyclic radical which isbonded via a nitrogen atom and may contain further heteroatoms and maybe aromatic;  aryl or hetaryl, each of which may be monosubstituted orpolysubstituted by C₁-C₁₈-alkyl, C₁-C₆-alkoxy, cyano, —CONHR² or—NHCOR²; R′ is C₂-C₃₀-alkyl, whose carbon chain may be interrupted byone or more —O— and/or —CO— groups and which may be monosubstituted orpolysubstituted by C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, whose carbon skeletonmay be interrupted by one or more —O— and/or —NR¹— groups and which maybe C₁-C₆-alkyl-substituted, and/or aryl, which may be substituted byC₁-C₁₈-alkyl or C₁-C₆-alkoxy;  methyl, which is monosubstituted ordisubstituted by aryl and/or C₅-C₈-cycloalkyl, each of which may besubstituted by C₁-C₁₈-alkyl or C₁-C₆-alkoxy;  C₅-C₈-cycloalkyl, whosecarbon skeleton may be interrupted by one or more —O— and/or —NR¹—groups and which may be monosubstituted or polysubstituted byC₁-C₆-alkyl.
 3. A rylene dye of the formula I as claimed in claim 1,where R is hydrogen;  C₁-C₃₀-alkyl, whose carbon chain may beinterrupted by one or more —O— and/or —CO— groups which may bemonosubstituted or disubstituted by C₁-C₆-alkoxy and/or aryl, which maybe substituted by C₁-C₁₈-alkyl or C₁-C₆-alkoxy;  aryl, which may bemonosubstituted or polysubstituted by C₁-C₁₈-alkyl, C₁-C₆-alkoxy and/orcyano; R′ is C₂-C₃₀-alkyl, whose carbon chain may be interrupted by oneor more —O— groups and which may be monosubstituted or polysubstitutedby C₁-C₆-alkoxy, C₅-C₈-cycloalkyl which may be C₁-C₆-alkyl-substituted,and/or aryl, which may be substituted by C₁-C₁₈-alkyl or C₁-C₆-alkoxy; methyl, which is monosubstituted or disubstituted by aryl and/orC₅-C₈-cycloalkyl, each of which may be substituted by C₁-C₁₈-alkyl orC₁-C₆-alkoxy;  C₅-C₈-cycloalkyl, which may be monosubstituted orpolysubstituted by C₁-C₆-alkyl.
 4. A process for the preparation of arylene dye of the formula I as claimed in claims 1 to 3, which comprisesa) reacting a bromorylene-3,4-dicarboximide of the general formula II

 with a benzophenonimine of the general formula III

 where R″, R′″, independently of one another, are hydrogen, C₁-C₆-alkylor C₁-C₆-alkoxy and x, y, independently of one another, are an integerfrom 1 to 3,  in the presence of an aprotic organic solvent, atransition-metal catalyst system and a base in an aryl-N couplingreaction, b) hydrolysing the resultant ketimine in the presence of anacid and in the presence of a polar, aprotic solvent to give anaminorylene-3,4-dicarboximide of the general formula IV

 and c) subsequently reacting the latter with a dicarbonate of thegeneral formula V

 in the presence of a polar, aprotic solvent and in the presence of abase to give a rylene dye I.
 5. A process for the preparation of anaminorylene-3,4-dicarboximide of the general formula IV

where R is hydrogen;  C₁-C₃₀-alkyl, whose carbon chain may beinterrupted by one or more —O—, —S—, —NR¹—, —CO— and/or —SO₂— groups andwhich may be monosubstituted or polysubstituted by cyano, C₁-C₆-alkoxy,aryl, which may be substituted by C₁-C₁₈-alkyl or C₁-C₆-alkoxy, and/or a5- to 7-membered heterocyclic radical which is bonded via a nitrogenatom and may contain further heteroatoms and may be aromatic;  aryl orhetaryl, each of which may be monosubstituted or polysubstituted byC₁-C₁₈-alkyl, C₁-C₆-alkoxy, cyano, —CONHR², —NHCOR² and/or aryl- orhetarylazo, each of which may be substituted by C₁-C₁₀-alkyl,C₁-C₆-alkoxy and/or cyano; R¹ is hydrogen or C₁-C₆-alkyl; R² ishydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each of which may besubstituted by C₁-C₆-alkyl, C₁-C₆-alkoxy and/or cyano; n is 2 or 3,which comprises a) reacting a bromorylene-3,4-dicarboximide of thegeneral formula II

 with a benzophenonimine of the general formula III

 in the presence of an aprotic organic solvent, a transition-metalcatalyst system and a base in an aryl-N coupling reaction, and b)hydrolysing the resultant ketimine in the presence of an acid and in thepresence of a polar, aprotic solvent.
 6. Anaminorylene-3,4-dicarboximide of the general formula IV

where R is hydrogen;  C₁-C₃₀-alkyl, whose carbon chain may beinterrupted by one or more —O—, —S—, —NR¹—, —CO— and/or —SO₂— groups andwhich may be monosubstituted or polysubstituted by cyano, C₁-C₆-alkoxy,aryl, which may be substituted by C₁-C₁₈-alkyl or C₁-C₆-alkoxy, and/or a5- to 7-membered heterocyclic radical which is bonded via a nitrogenatom and may contain further heteroatoms and may be aromatic;  aryl orhetaryl, each of which may be monosubstituted or polysubstituted byC₁-C₁₈-alkyl, C₁-C₆-alkoxy, cyano, —CONHR², —NHCOR² and/or aryl- orhetarylazo, each of which may be substituted by C₁-C₁₀-alkyl,C₁-C₆-alkoxy and/or cyano; R¹ is hydrogen or C₁-C₆-alkyl; R² ishydrogen, C₁-C₁₈-alkyl; aryl or hetaryl, each of which may besubstituted by C₁-C₆-alkyl, C₁-C₆-alkoxy and/or cyano; n is 2 or
 3. 7.The use of a rylene dye of the formula I as claimed in claims 1 to 3 forcoloring high-molecular-weight organic and inorganic materials.
 8. Theuse as claimed in claim 7, wherein plastics, surface coatings, printinginks and oxidic layer systems are colored.
 9. The use as claimed inclaim 8 or 9, wherein laser-markable and laser-inscribable colorings areproduced.